CN101531587B - Zirconium lead tartrate double metal salt, preparation method and application thereof - Google Patents
Zirconium lead tartrate double metal salt, preparation method and application thereof Download PDFInfo
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- CN101531587B CN101531587B CN2009100213806A CN200910021380A CN101531587B CN 101531587 B CN101531587 B CN 101531587B CN 2009100213806 A CN2009100213806 A CN 2009100213806A CN 200910021380 A CN200910021380 A CN 200910021380A CN 101531587 B CN101531587 B CN 101531587B
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- metal salt
- zirconium
- tartrate
- double metal
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Abstract
The invention discloses a zirconium lead tartrate double metal salt comprising ZrPb2(C4H2O6).2nH2O, wherein the C4H2O6 is a tartaric acid negative ion; and n is coordinated water and/or the number of crystal water in the zirconium lead tartrate double metal salt, and n is equal to 0 to 2. The preparation method of the zirconium lead tartrate double metal salt comprises the following steps: (1) reacting tartaric acid and soluble lead salt to obtain lead tartrate; (2) adding an alkali solution into the lead tartrate, and filtering the mixture; and (3) dissolving soluble zirconium salt into water, and adding the filtrate obtained in the step (2) to obtain zirconium lead tartrate. The zirconium lead tartrate double metal salt can be used as a combustion catalyst of a solid propellant, an unstable combustion inhibitor and a difunctional ballistic modifier.
Description
Technical field
The present invention relates to a kind of Zirconium lead tartrate double metal salt and preparation method thereof, this bimetal salt both can be used as the combustioncatalysts of SP, also can be as the suppressor factor of SP unstable combustion.
Technical background
SP is the energy of solid propellant rocket, has been widely used in strategy, tactical weapon and the spationautics.The range of rocket and flight velocity at first depend on the total energy level of propellant charge, yet closely related with the energy release rate and the efficient thereof of propellant charge again.And discharge the combustion processes of means as the propelling agent energy, and the branch of stable state combustion and unstable combustion is arranged, be one of propelling agent important subject of developing personnel for a long time therefore to the property regulation of stable state combustion and to the inhibition of unstable combustion always.
Double-basis be SP general adopt inorganic or organic metal salt as combustioncatalysts.Discover that the catalytic effect of lead salt is superior to other metal-salt, the catalytic effect of organic lead-salt is superior to inorganic lead salt; This is because the organic carboxyl acid lead salt exists conjugation and inductive effect; The easy decomposition, and the organo-lead compound pyrolysis produces uniformly, the lead of nascent state and oxide compound thereof be as main catalytic active component, makes its good catalytic activity; Organic lead-salt not only can improve the combustion speed that double-basis is a propelling agent, and can effectively reduce the pressure index that double-basis is a propelling agent.
The domestic maximum unstable combustion suppressor factor that uses is Al powder and Al
2O
3Problems such as the propelling agent energy is low though the adding of Al powder has solved, HF oscillation unstable combustion; But aluminium powder has been participated in combustion reactions when propellant combustion; The mover ballisticperformances is affected adversely, the more important thing is at the jet pipe afterbody to produce dense plumage cigarette, this and modern weapons requirement propelling agent have low signature and are not inconsistent.And Al
2O
3Because its fusing point is lower, be prone to during burning be condensed into macroparticle with catalyst P bO, CuO etc., influence is to the inhibition efficient of unstable combustion.ZrO
2Zirconium thing substitute for Al powder and Al
2O
3, not only can fine inhibition double-basis the unstable combustion that is propelling agent, and the mover ballisticperformances had no adverse effect.
Summary of the invention
One of the object of the invention provides a kind of Zirconium lead tartrate double metal salt;
Another object of the present invention provides the compound method of above-mentioned Zirconium lead tartrate double metal salt;
A further object of the invention provides the application of above-mentioned Zirconium lead tartrate double metal salt as combustioncatalysts, unstable combustion suppressor factor and difunctional ballistic-modifiers.This bimetal salt is to play difunctional effect (katalysis and unstable combustion restraining effect) in the propelling agent in double-basis, and is guidance and stealthy very favourable a kind of difunctional ballistic-modifiers to guided missile.
Implementation procedure of the present invention is following:
The Zirconium lead tartrate double metal salt of formula (I) expression:
ZrPb
2(C
4H
2O
6)
2·nH
2O (I)
Wherein, C
4H
2O
6Be the tartrate negatively charged ion;
N is the number of coordinated water and/or crystal water in the complex molecule, n=0～2.
Obviously, coordinated water and/or crystal water are all sloughed in the Zirconium lead tartrate double metal salt heating, then n=0 does not slough or not exclusively sloughs coordinated water and/or crystal water, then n=0～2.
The preparation method of Zirconium lead tartrate double metal salt comprises the steps:
(1) tartrate is sloughed half proton approximately with alkali reaction earlier, obtains the white precipitate lead tartrate with the dissoluble lead reactant salt again, and described alkali is NaOH, KOH, Na
2CO
3, NaHCO
3Or ammoniacal liquor;
(2) in lead tartrate, adding strong base solution is 8～9 until pH, crosses to filter colourless solution;
(3) the solubility zirconates is water-soluble, the colourless solution that adding step (2) makes gets the white precipitate Zirconium lead tartrate.
Advantage of the present invention and positively effect:
Synthesis technique of the present invention is simple, and the synthetic Zirconium lead tartrate double metal salt decomposition generation that obtains is uniform, the lead and the main catalytic active component of oxide compound conduct thereof of nascent state, utilizes the dystectic ZrO of Zirconium lead tartrate double metal salt decomposition generation
2As promotor, can further improve catalytic effect, simultaneously, ZrO
2Can play the effect that suppresses unstable combustion well as dystectic unstable combustion suppressor factor, therefore, Zirconium lead tartrate double metal salt can be used as difunctional ballistic-modifiers.
Description of drawings
Fig. 1 contains the combustion speed-pressure curve of Zirconium lead tartrate double-base propellent;
Fig. 2 Zirconium lead tartrate is to the catalytic efficiency (-pressure curve of double-base propellent;
Fig. 3 contains the combustion speed-pressure curve of Zirconium lead tartrate composite modified double base propellant;
Fig. 4 Zirconium lead tartrate is to the catalytic efficiency (-pressure curve of composite modified double base propellant.
Embodiment
The preparation method of Zirconium lead tartrate double metal salt comprises the steps:
(1) getting mol ratio respectively is 1: 1 tartrate and sodium hydrogencarbonate, and tartrate is dissolved in the zero(ppm) water, under violent stirring, sodium hydrogencarbonate is slowly joined in the tartaric acid solution, about reaction 15min, filter, colourless solution.
(2) getting with the tartrate mol ratio is 1.1: 1 lead nitrate, is dissolved in a certain amount of zero(ppm) water, when water temperature rises to 80 ℃, slowly adds step (1) colourless solution, stirs 3～4h, obtains white precipitate.
(3) white precipitate that step (2) is obtained is used hot distilled water wash 3～5 times, uses absolute ethanol washing again 2 times, suction filtration, and drying is ground, and gets white powder (lead tartrate).
(4) getting mol ratio respectively is 2: 1 NaOH and lead tartrate powder, in white powder, adds a certain amount of zero(ppm) water, and ultrasonic making it is uniformly dispersed, and under 60 ℃, intensively stirred condition, slowly splashes into NaOH solution, and pH is 8～9, filter, colourless solution.
(5) getting with the lead tartrate mol ratio is 1.1: 1 Zircosol ZN, is dissolved in a certain amount of zero(ppm) water, under 80 ℃, intensively stirred condition; In the colourless solution that slowly adding step (4) obtains, 80 ℃ of insulation 3～4h get white precipitate; Use hot distilled water wash 3～5 times, use absolute ethanol washing again 2 times, suction filtration; Drying is ground, and gets white powder (Zirconium lead tartrate).
The sign of Zirconium lead tartrate double metal salt
1. ultimate analysis
The observed value of each element is (%): C 12.68, and H 1.41, O24.51, and each element theory calculating content is (%): C11.78 in the target compound, and H0.98, O 27.48.
2.X fluorescent x ray spectroscopy x
The observed value that X-ray fluorescence spectra is analyzed metal is (%): Zr 12.78, and Pb 48.62, and the calculated value of metal content is (%): Zr 11.17 in the target compound, and Pb 48.59, and the molecular formula and the ZrPb of target compound is described
2(C
4H
2O
6)
2NH
2O is consistent.
3. infrared analysis
Infrared analysis shows, compares with tartrate acid, in the lead tartrate collection of illustrative plates, belongs to the 1739cm of carboxylate radical
-1(υ
-C=O) disappear, the 1372cm of carboxylate salt appears belonging to
-1(υ
s -COO) and 1591cm
-1(υ
As -COO) two new peaks, show that carboxylate radical reacts to have generated carboxylate salt and belong to the 1295cm of the tertiary alcohol
-1(δ
O-H) and 1141cm
-1(υ
C-O) move to 1300cm respectively
-1And 1129cm
-1, and in the collection of illustrative plates of Zirconium lead tartrate, compare with the lead tartrate collection of illustrative plates, belong to tertiary alcohol 1300cm
-1And 1129cm
-1Disappear, explain that alcoholic extract hydroxyl group reacts, and broad peak 3457cm
-1Belong to the hydroxyl in the crystal water.
4.TG analyze
The TG analysis revealed has two weightless steps, and is weightless 2.19% at 100 ℃～200 ℃, this with lose a crystal water and conform to, weightless 23.31% at 200 ℃～600 ℃, residual volume is 70.95% at last, this and PbO+ZrO
2(67.85%) originally conforms to a spot of carbon back.
Above-mentioned analysis revealed, the possible structural formula of the synthetic Zirconium lead tartrate double metal salt that obtains is following:
(1) Zirconium lead tartrate is the influence of propellant burning property to double-basis
Adopt the basic components of double-base propellent sample to be in the experiment: double-basis tamanori 89%, 8.5%, No. two centralite (C of diethyl phthalate (DEP)
2) 2.0%, Vaseline (V) 0.5%, dose are pressed the 500g batching, and catalyzer adds.Adopt the basic components of composite modified double base propellant sample to be: double-basis tamanori 66%, RDX (RDX) 26%, Ji receives 5%; Other auxiliary agent 3%, dose are pressed the 500g batching, and catalyzer adds; Contrast blank propelling agent sample and do not add catalyzer, other component is identical with content.SP adopt absorptions-expelling water-put ripe-the conventional solvent-free moulding process that rolls-be cut into medicinal strip prepares.
Combustion speed is measured equipment used and is the fast appearance of combustion; Adopt target collimation method specimen combustion speed, the little powder column of the Φ 5 * 15mm side of having handled is coated 6 times with the polyvinyl alcohol solution dipping and dries, then test combustion speed in the fast appearance of combustion; Experimental temperature is 20 ℃, pressure range 2MPa～22MPa.
In Fig. 1～Fig. 4, u is combustion speed, and P is a pressure, η
rBe efficiency of combustion (it is meant the ratio of the propellant burning rate that contains catalyzer under the uniform pressure and blank propellant burning rate) that a is the double-basis blank formula, b is the double-base propellent prescription that contains Zirconium lead tartrate; C is the composite modified double base propellant blank formula, and d is the composite modified double base propellant prescription that contains Zirconium lead tartrate, as can be seen from the figure; In double-base propellent, the Zirconium lead tartrate of adding 3% can obviously improve double-base propellent combustion speed, in 2～22MPa scope; Efficiency of combustion is more than 1.3, and can obviously reduce burning rate pressure exponent in the mesohigh section, in 12～16MPa scope; Burning rate pressure exponent n=0.24, linearly dependent coefficient r=0.9879.And in the RDX-CMDB propelling agent, add 3% Zirconium lead tartrate, double-base propellent combustion speed can be obviously improved equally, and burning rate pressure exponent can be obviously reduced in the mesohigh section; In 2～12MPa scope, efficiency of combustion is more than 1.3, in 10～16MPa scope; N=0.25, r=0.9930.
(2) Zirconium lead tartrate is to the inhibition effect of composite modified double base propellant unstable combustion
Utilize the controlled T shape of pressure burner measuring stress coupling response function, used propellant formulation is with last identical, and the propelling agent test specimen is that diameter is the disk shape of 50mm; Thickness is respectively the sample of the disk propelling agent test specimen of 6mm and 9mm as a test; And coat with the acetone soln of nitro oil-varnished cambric, priming charge mixes with No. 2 black powders and body medicine end, and black powder is 1g; The body medicine is between 3～7g, and the propelling agent response function data of acquisition are as shown in table 1.
Can find out from table 1, compare that the oscillation pressure scope that contains the Zirconium lead tartrate propelling agent is very little, only in 1.5MPa～2MPa scope, produce vibration, but stable burning below 1.12MPa in 1.48～1.91MPa scope, produces vibration with blank formula.When pressure was 1.91MPa, it was the strongest to vibrate, and the coupling pressure response function is 3.49MPa; Rising along with pressure; Vibration weakens, and response function reduces, when pressure reaches 2.56MPa when above; Vibration disappears, the adding of this explanation Zirconium lead tartrate to the RDX-CMDB propelling agent unstable combustion played good inhibitory effect.
Table 1 propelling agent response function data
Claims (5)
1. the Zirconium lead tartrate double metal salt of structural formula (I) expression:
2. the preparation method of the said Zirconium lead tartrate double metal salt of claim 1 comprises the steps:
(1) tartrate is sloughed half proton with alkali reaction earlier, obtains the white precipitate lead tartrate with the dissoluble lead reactant salt again;
(2) in lead tartrate, adding strong base solution is 8～9 until pH, crosses to filter colourless solution;
(3) the solubility zirconates is water-soluble, add step (2) filtrate Zirconium lead tartrate.
3. according to the preparation method of the said Zirconium lead tartrate double metal salt of claim 2, it is characterized in that: described alkali is NaOH, KOH, Na
2CO
3, NaHCO
3Or ammoniacal liquor.
4. the said Zirconium lead tartrate double metal salt of claim 1 is as the application of the combustioncatalysts of SP.
5. the said Zirconium lead tartrate double metal salt of claim 1 is as the application of SP unstable combustion suppressor factor.
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| CN102993002B (en) * | 2012-12-20 | 2014-10-22 | 西安近代化学研究所 | 3, 4-dihydroxy benzoic acid Cu-Zr double metal salts and preparation method and application thereof |
| CN103626696A (en) * | 2013-12-04 | 2014-03-12 | 西安近代化学研究所 | Citrazinic acid copper zirconium bimetallic salt as well as preparation method and application thereof |
| CN103641777A (en) * | 2013-12-04 | 2014-03-19 | 西安近代化学研究所 | Citrazinic acid lead-zirconium double metal salts and preparation method and application thereof |
| CN104119403B (en) * | 2014-08-04 | 2017-01-18 | 西安近代化学研究所 | Copper zirconium tartrate compound as well as preparation method and use thereof |
| CN110669068B (en) * | 2019-11-05 | 2022-09-16 | 湖南工业大学 | Method for recycling waste zirconium balls and preparing combustion catalyst |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85100236A (en) * | 1985-04-01 | 1986-07-16 | 武汉大学 | The preparation method of the lead-iron bi-metal complex that one class is novel |
-
2009
- 2009-03-04 CN CN2009100213806A patent/CN101531587B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85100236A (en) * | 1985-04-01 | 1986-07-16 | 武汉大学 | The preparation method of the lead-iron bi-metal complex that one class is novel |
Non-Patent Citations (2)
| Title |
|---|
| 李青.酒石酸铅纳米粉体的制备及表征.《中国硅酸盐学会2003年学术年会论文摘要集》.2003,437. * |
| 赵凤起.用于双基系固体推挤剂的非铅催化剂的研究与发展动向.《飞航导弹》.1993,(第8期),28-31. * |
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